Wyniki wyszukiwania - Biblioteka Nauki

1

Spektroskopia EPR w biopomiarach płynności lipidów błonowych

100%

Żakowska I. , Jóźwik K. , Gwoździński K. , Olejniczak J. , Pawlicki L.

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tom z. 98

471-475

PL

W referacie przedstawiono metodyką biopomiarów płynności lipidów błonowych metodą spektroskopii elektronowego rezonansu paramagnetycznego (EPR). Zastosowano trzy znaczniki spinowe 5-, 12- oraz kwas 16-doksylostearynowy, które lokują się na różnych głębokościach lipidów błonowych. Wykazano istotny statystycznie (odpowiednio: p < 0,01; p < 0,001) wzrost płynności lipidów błonowych w płytkach krwi pochodzących od osób z chorobą niedokrwienną serca w głębszych regionach łańcucha węglowodorowego kwasu stearynowego.

EN

The methodology of biomeasurements of lipid membrane fluidity using electron paramagnetic resonance (EPR) spectroscopy has been shown. Three spin labelled fatty acids: 5-, 12- and 16-doxylstearic acid, which are located at different depths in the lipid membrane have been used. The blood was taken from ischaemic heart disease (IHD) patients. Results showed a significant increase (p < 0,01; p < 0,001 respectively) in lipid membrane fluidity of human blood platelets in deeper regions of hydrocarbon chains of stearic acid.

2

Electron paramagnetic resonance studies on silver atoms and clusters in regularly interstratified clay minerals

100%

Yamada H. , Sadlo J. , Tamura K. , Shimomura S. , Turek J. , Michalik J.

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tom Vol. 49, nr 4

131-136

EN

The formation and stabilization of reduced silver species in the regularly interstratified clay minerals, trioctahedral smectite/chlorite (tri-Sm/Ch) and dioctahedral smectite/mica (di-Sm/M), have been studied by electron paramagnetic resonance (EPR) spectroscopy. Both minerals loaded with Ag+ cations after degassing and dehydration were g-irradiated at 77 K and monitored by EPR as the temperature increased. Some samples were exposed to water or methanol vapor after dehydration. In both hydrated and dehydrated samples only the doublets assigned to Ag0 atoms were observed with no evidence of the formation of Ag clusters. However, the EPR parameters of silver atoms in both matrices are different. In tri-Sm/Ch the narrow anisotropic EPR lines overlap with the broader isotropic lines, whereas in di-Sm/M only broad lines are recorded. The hyperfine splitting - Aiso(Ag0) is larger in tri-Sm/Ch than in di-Sm/M. Also the stability of Ag0 in both clay minerals is distinctly different. Ag0 doublet in di-Sm/M disappears completely above 230 K, whereas in tri-Sm/Ch it is still recorded at 310 K. It is proposed, basing on the EPR results that Ag0 atoms appear at different sites in both matrices: - in tri-Sm/Ch in the middle of smectite interlayer and in hexagonal cavities in the silicate sheets of tetrahedron layer and in di-Sm/M in hexagonal cavities only. When samples had been exposed to methanol before irradiation, the silver clusters become stabilized in the interlayer sites. In tri- Sm/Ch matrix the silver dimer Ag2+ formed by g-irradiation at 77 K is transformed to tetrameric cluster, Ag43+ at 150 K. In di-Sm/M the radiation-induced silver agglomeration proceeds in a similar way, but with a slower rate and Ag tetramer is formed only above 190 K. In both clay minerals, Ag43+ clusters decay above 250 K.

3

EPR examination of free radicals thermally formed in vaselinum flavum

100%

Ramos P. , Pilawa B.

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tom Vol. 60, No. 3, part 1

443--447

EN

The popular pharmaceutical base used in pharmacy – vaselinum flavum – was studied by an X-band (9.3 GHz) EPR spectrometer in the range of microwave power of 2.2–70 mW. The samples were sterilized in hot air oven at temperatures: 160°C (120 min), 170°C (60 min), and 180°C (30 min). The aim of this work was to determine properties and free radical concentrations in vaselinum flavum thermally sterilized at different conditions. The changes in free radical system in vaselinum flavum during storage were analyzed. Free radicals were found in all the heated samples. The lowest free radical concentration was obtained for vaselinum flavum heated at 180°C for 30 min; so these parameters are proposed for the thermal sterilization of this pharmaceutical base. Interactions with oxygen decreased free radical concentration in vaselinum flavum during storage. Strong quenching of free radicals in vaselinum flavum was observed after 2 days for the samples sterilized at temperatures 160 and 180°C. Such an effect for vaselinum flavum heated at temperature 170°C was observed later, 13 days after sterilization. Fast spin-lattice relaxation processes exist in thermally sterilized vaselinum flavum. The EPR lines of heated vaselinum flavum were homogeneously broadened. EPR spectroscopy and its use for examining the thermal sterilization process in pharmacy was confirmed.

4

Preparation of N-aryl-ketonitrone spin traps

88%

Hassan I. , Lauricella R. , Tuccio B.

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tom 4

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nr 2

338-350

EN

The syntheses of seven N-aryl-C,C-dialkoxycarbonylnitrones 1–7, six of which were original, were achieved from the appropriate aryl-nitroso compounds. These ketonitrones were found to trap efficiently carbon-centred free radicals in aqueous media, yielding stable aminoxyl radicals whose EPR spectra lasted several days. The two penta-deuterated compounds 6 and 7 were also found to be efficient at trapping methoxyl radical. Their various spin adducts showed simple three line signals, very sensitive to the polarity of the environment. This study represents the very first use of linear ketonitrones as spin traps.

5

THE INFLUENCE OF STORAGE TEMPERATURE AND UV-IRRADIATION ON FREE RADICAL SCAVENGING PROPERTIES OF ETHANOLIC EXTRACTS OF PROPOLIS

88%

Komosińska-Vassev K. , Olczyk P. , Ramos P. , Mencner L. , Derkacz A. , Waluga E. , Krysik K. , Olczyk K. , Pilawa B.

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nr 6

1833-1840

EN

The free radical scavenging activity of ethanolic extracts of propolis (EEP) at the concentrations of 3%, 7%, and 10% was examined. The impact of storage temperature and exposure to ultraviolet (UV) light on the interactions of extracts of propolis with the model DPPH free radicals was also determined. The quenching of an X-band electron paramagnetic resonance spectra of DPPH free radicals by the extracts stored at room temperature, heated at the temperature of 50 oC and exposed to UV-irradiation, were compared. The examined propolis ethanolic extracts revealed an antioxidative character. The storage of the samples at a higher temperature (50 oC) caused a decrease of the scavenging activity equaling to 7% and 10% EEP. UV-irradiation of the 3% EEP increased the quenching of DPPH free radical lines. The reverse effect was observed for the 7% and 10% propolis extracts. The 3% ethanolic extract of propolis is more stable for storage at 50ºC, and less than other analyzed EEP susceptible for UV-irradiation. Alterations of the antioxidative properties of the analyzed EEP and changes in the kinetics of their interactions with free radicals, indicate that 3%, 7%, and 10% propolis extracts should not be exposed to the temperature of 50 oC and UV-irradiation.

6

Effect of UV irradiation on free radicals in synthetic melanin and melanin biopolymer from Sepia offi cinalis : EPR examination

88%

Zdybel M. , Pilawa B.

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tom Vol. 60, No. 3, part 1

483--488

EN

Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR) spectroscopy. The effect of time of ultraviolet (UV) irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz) in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~1021–1022 spin/g) of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.

7

Oxygen influence on EPR spectra of carbon materials

75%

Stelmakh V. , Stryhutski L. , Shpilevsky E. , Żukowski P. , Karwat C.

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tom Vol. 44, nr 4

227-234

EN

A model of the effects of paramagnetic oxygen molecules as centres of short relaxation times on paramagnetic carbon centres has been developed. A "Relay-race mechanism" concept has been proposed within which changes are considered from the viewpoint of the character of an interaction between carbon centres induced by oxygen molecules. The model accounts for literature data concerning on anomalous decrease of recorded intensity during oxygen molecule input. A possibility of the formation of a superlorentz line form, characterised by shallower slope of the wings as compared to the lorentz line has been demonstrated. Quantitative parameters for the line form analysis have been introduced.

8

Effects of storage conditions on formation of free radicals in soybean extract – an EPR spectroscopy study

75%

Jarco S.

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2017

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tom 71

217-224

EN

OBJECTIVE: Soybean extract is a valuable food supplement used for the prevention of cancer and other purposes. The role of free radicals in carcinogenesis has been proven. Studies have also confirmed the effect of storage conditions on the formation of free radicals in natural medicinal products. The study presents an attempt to optimize the storage conditions of soybean extract to prevent the formation of free radicals. AIM OF THE STUDY: The aim of the study was to determine the effect of temperature and UV radiation on the formation of free radicals in soybean extract during storage. MATERIAL AND METHODS: Samples of soybean extract were heated to temperatures of 30, 40 and 50°C. Subsequent samples were exposed to UV radiation (wavelengths 315–400 nm) for 30 and 60 minutes. EPR (electron paramagnetic resonance) spectroscopy was used to analyse the amplitude and linewidth of the EPR signal and to calculate the concentration of free radicals in the samples. RESULTS: At a room temperature of 25°C and in the absence of light, no EPR signal was recorded for the tested samples. Heating and exposure to UV light caused the formation of free radicals in the samples. The highest concentration of free radicals was found in the sample exposed to UV light for 60 minutes, while the lowest was in the sample heated to 30°C. CONCLUSIONS: The use of EPR spectroscopy enabled the identification of optimal storage conditions for soybean extract, i.e. 25°C and darkness.

PL

WSTĘP: Cennym uzupełnieniem diety jest wyciąg z nasion soi, wykorzystywany między innymi w profilaktyce nowotworów. Udział wolnych rodników w procesach karcynogenezy został udowodniony. Badania potwierdzają wpływ warunków przechowywania naturalnych środków leczniczych na zachodzące w nich zjawiska wolnorodnikowe. W pracy podjęto próbę optymalizacji warunków przechowywania wyciągu z nasion soi, aby zapobiec powstawaniu w nim wolnych rodników. CEL PRACY: Celem pracy było określenie wpływu temperatury i promieniowania UV na generowanie wolnych rodników w wyciągu z nasion soi w trakcie przechowywania. MATERIAŁ I METODY: Próbki z wyciągiem z nasion soi ogrzewano w temperaturach 30, 40 i 50°C. Kolejne próbki naświetlano promieniowaniem UV (długość fali 315–400 nm) przez 30 i 60 minut. Wykorzystano spektroskopię EPR (elektron paramagnetic resonance), analizując amplitudę i szerokość linii EPR oraz obliczając koncentrację wolnych rodników w próbkach. WYNIKI: W temperaturze pokojowej 25°C oraz przy braku dostępu światła nie rejestrowano sygnału EPR dla testowanych próbek. Ogrzewanie próbek oraz ekspozycja na promieniowanie UV powodowały pojawienie się w nich wolnych rodników. Największą koncentrację wolnych rodników stwierdzono w próbce naświetlanej UV przez 60 minut, najniższe zaś w próbce ogrzanej do 30°C. WNIOSKI: Wykorzystanie spektroskopii EPR pozwoliło na ustalenie optymalnych warunków przechowywania wyciągu z nasion soi, którymi są temperatura 25°C oraz brak dostępu światła.

9

EPR study of free radicals formed in fusidic acid and neomycin under UV irradiation

75%

Pierzchała E. , Ramos P. , Pilawa B.

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nr 2

215-223

EN

Free radicals in UV irradiated antibiotics used in dermatology were examined. Concentrations of free radicals in fusidic acid and neomycin, were determined. EPR spectra of the tested antibiotics were measured by electron paramagnetic resonance spectrometer with magnetic modulation of 100 kHz and numerical acquisition system the Rapid Scan Unit. The influence of microwave powers in the range of 2.2-70 mW on the spectra was obtained. Amplitudes (A) and linewidths (ΔBpp) of the EPR spectra, were analysed. The EPR spectra were homogeneously broadened. Fast spin-lattice relaxation processes existed in UV irradiated fusidic acid and neomycin, which EPR spectra were not saturated up to 70 mW. The influence of the time of UV irradiation on free radicals in the samples was observed. The samples were irradiated by UVA (315-400 nm) in the 30, 60, and 90 minute period. Free radical concentrations in the tested antibiotics exposed to UV were proportional to the amplitudes (A) of the EPR spectra. The highest amplitudes (A) were observed for the UV irradiated antibiotics during 60 minutes. The higher amplitudes (A) characterized fusidic acid than neomycin. Fusidic acid and neomycin used to treat bacterial infection of skin under UV irradiation may produce free radical toxic effects. The stronger photosensitivity characterized fusidic acid relatively to neomycin. EPR spectroscopy is the useful method to examine free radicals formed in antibiotics during photolysis.

10

Action of Some Organomercury Compounds on Photosynthesis in Spinach Chloroplasts

75%

Šeršeň F. , Kráľová K.

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tom 20

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nr 3

489-498

EN

The effects of five organomercury compounds (methylmercuric chloride, phenylmercuric acetate, phenylmercuric borate, phenylmercuric citrate and diphenylmercury) on photosynthetic electron transport (PET) in spinach chloroplasts were investigated. The IC50 values of organomercury compounds related to PET inhibition in spinach chloroplasts varied in the range from 468 mmol dm-3 to 942 mmol dm-3 and were approximately by one order higher than the corresponding value determined for HgCl2 applied also in DMSO solution (IC50 = 58 mmol dm-3). Due to extremely low aqueous solubility of diphenylmercury, the corresponding IC50 value could not be determined. Using EPR spectroscopy as probable sites of action of organomercury compounds in photosynthetic apparatus ferredoxin on the acceptor side of PS 1 and the quinone electron acceptors QA or QB on the reducing side of PS 2 were suggested.

PL

Zbadano wpływ pięciu związków rtęcioorganicznych (chlorku metylortęci, octanu fenylortęci, boranu fenylortęci, cytrynianu fenylortęci i difenylortęci) na fotosyntetyczny transport elektronów (PET) w chloroplastach szpinaku. Wartości IC50 dla związków rtęcioorganicznych związanych z inhibicją PET w chloroplastach szpinaku zmieniała się w zakresie od 468 do 942 μmol dm-3 i była w przybliżeniu o rząd większa od odpowiedniej wartości określonej dla HgCl2, stosowanego również w roztworze DMSO (IC50 = 58 μmol dm-3). Ze względu na bardzo małą rozpuszczalność difenylortęci w wodzie odpowiednia wartość IC50 nie może być określona. Wyniki badań za pomocą spektroskopii EPR pozwoliły na zaproponowanie prawdopodobnych miejsc działania związków rtęci w procesie fotosyntezy ferredoksyny po stronie akceptora PS 1 i chinonowego akceptora elektronów QA lub QB po stronie redukującej PS 2.

11

Multifrequency EPR study on radiation induced centers in calcium carbonates labeled with 13C

75%

Sadło J. , Bugaj A. , Strzelczak G. , Sterniczuk M. , Jaegermann Z.

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tom Vol. 60, No. 3, part 1

429--434

EN

In calcite and aragonite, γ-irradiated at 77 K, several paramagnetic centers were generated and detected by EPR spectroscopy; in calcite, CO3 – (orthorhombic symmetry, bulk and bonded to surface), CO3 3–, NO3 2–, O3 –, and in aragonite CO2 – (isotropic and orthorhombic symmetry) depending on the type of calcium carbonate used. For calcium carbonates enriched with 13C more detailed information about the formed radicals was possible to be obtained. In both natural (white coral) and synthetic aragonite the same radicals were identifi ed with main differences in the properties of CO2 – radicals. An application of Q-band EPR allowed to avoid the signals overlap giving the characteristics of radical anisotropy.

12

Zastosowanie spektroskopii EPR do badania deksametazonu sterylizowanego termicznie

75%

Kościelniak M. , Pilawa B. , Wilczyński S.

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2008

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tom Vol. 11, no. 81-84

55--56

PL

Spektroskopię elektronowego rezonansu paramagnetycznego (EPR) zastosowano do oceny optymalnych warunków sterylizacji deksametazonu. Sterylizację sproszkowanego leku wykonano w suchym powietrzu w temperaturze 180°C w czasie wynoszącym 30 minut. Celem pracy jest określenie właściwości wolnorodnikowych sterylizowanego deksametazonu. Optymalnym warunkom sterylizacji powinno towarzyszyć powstawanie niewielkiej ilości wolnych rodników w substancji leczniczej, które mogą powodować szereg efektów ubocznych podczas farmakoterapii. Deksametazon jest syntetycznym glikokortykosteroidem z grupy hormonów steroidowych. Wykazuje silne działanie przeciwzapalne i immunosresyjne. Jest silniejszy ok. 20-30 -krotnie przewyższając hydrokortyzon i 4-5 krotnie niż prednizolon. Deksametazon hamuje zapalenie i obrzęk tkanki, dlatego jest używany do leczenia zapaleń o szerokim zakresie chorób auto-immunologicznych takich zapalenie stawów itp. Jest również aplikowany małych ilościach przed lub po zabiegach dentystycznych. W onkologii deksametazon jest podawany w trakcie chemioterapii [1,2]. Strukturę chemiczną deksametazonu przedstawiono na RYSUNKU 1. Pomiary widm wykonano za pomocą spektrometru EPR Firmy RADIOPAN (Poznań) przy modulacji pola magnetycznego wynoszącej 100kHz. Częstotliwość promieniowania mikrofalowego wynosiła 9.3GHz. Widma EPR w postaci pierwszej pochodnej rejestrowano w szerokim zakresie mocy mikrofalowej 0.7- 70mW. Analizowano parametry widm EPR oraz koncentrację wolnych rodników w sterylizowanym leku. Zbadano zmiany koncentracji i parametrów widm EPR wraz ze wzrostem czasu przechowywania leku sterylizowanego w 180°C przez 30 minut. Wyznaczono zależność amplitudy i szerokości linii EPR od mocy mikrofalowej. Analizowano wpływ mocy mikrofalowej na kształt i asymetrię widm EPR. Próbki deksametazonu nie poddane działaniu wysokiej temperatury nie dawały sygnału EPR. Widma EPR deksametazonu sterylizowanego w 180°C przez 30 minut wykazywały złożony charakter (RYS.2). Wskazuje to, że w sterylizowanym deksametazonie występuje kilka rodzajów wolnych rodników. Rejestrowane widma EPR stanowią superpozycję linii składowych pochodzących od poszczególnych typów wolnych rodników. Zbadano wpływ mocy mikrofalowej na amplitudę i szerokość linii EPR termicznie sterylizowanego deksametazonu. Zaobserwowano zmianę kształtu widm EPR wraz z mocą mikrofalową. Wraz ze wzrostem mocy mikrofalowej rośnie amplituda linii EPR deksametazonu. Podobną zależność zarejestrowano dla szerokości linii EPR. Taki charakter zamian wskazuje na jednorodne rozmieszczenie centrów paramagnetycznych w termicznie sterylizowanym deksametazonie (RYS. 3 i 4). Linie EPR różnych grup wolnych rodników nasycają się przy innej mocy mikrofalowej. Wolne rodniki w sterylizowanym deksametazonie są stabilne. Nie obserwowano szybkiego zaniku wolnych rodników z czasem przechowywania próbki. Badania EPR wskazują na niewielką zależność asymetrii linii EPR od mocy mikrofalowej. Moc mikrofalowa nieznacznie wpływa na wszystkie analizowane parametry IA1-A2I, IA1/A2I, IB1-B2I, IB1/B2I wyznaczone w pracy w celu oceny asymetrii linii EPR.

EN

Electron paramagnetic resonance (EPR) spectroscopy was applied to examine optimal sterilization conditions of dexamethasone. Sterilization of powdered dexamethasone was done in dry air at temperature 180°C during the time of 30 minutes. The aim of this work was to determine free radical properties of sterilized dexamethasone. It is expected that optima conditions of sterilization is accompanied by formation of low amount of free radicals in drug which can cause many side effects during pharmacotherapy. Dexamethasone is a potent synthetic member of the glucocorticoid class of steroid hormones. It acts as an anti-inflammatory and immunosuppressant. Its potency is about 20-30 times that of hydrocortisone and 4-5 times of prednisone. Dexamethasone inhibit the inflammatory and the edema of the tissue, so its making useful for the treatment of a wide range of inflammatory and auto-immune conditions such as rheumatoid arthritis ect. It is also given in small amounts before and/or after some forms of dental surgery. In oncology dexamethasone, it is given to cancer patients undergoing chemotherapy [1,2]. Chemical structure of dexamethasone is presented in FIGURE 1. Measurements of spectra were done by the use of EPR spectrometer produced by RADIOPAN Firm (Poznań) with modulation of magnetic field of 100 kHz. Microwave frequency of 9.3GHz was applied. The first-derivative EPR spectra were recorded with microwave power of the wide range of 0.7-70mW. Parameters of EPR spectra and free radical concentration in the sterilized drug were analyzed. Changes of free radical concentration and EPR parameters with increasing of storage time after heating of the drug at 180°C were evaluated. Changes of amplitud es and linewidths of EPR spectra with microwave power were determined. The influence of microwave power on lineshape of EPR spectra and line asymmetry was analyzed. Samples of dexamethasone not heated with high temperature gave no EPR signals. EPR spectra of dexamethasone sterilized in 180°C during 30 minutes reveal complex structure (FIG. 2). It was stated that several types of free radicals exist in the sterilized drug. Its EPR spectra reveal multi-component structure. The recorded EPR spectra are superposition of component lines of the individual types of free radicals. Influence of microwave power on amplitude and linewidths thermally sterilized dexamethasone was tested. Changes of EPR lineshapes with microwave power were observed. Amplitude of EPR line increase with microwave power increasing. Similar relationship for linewidths of EPR lines was recorded. This kind of relationship evidence on homogenous location of paramagnetic centers in thermally sterilized dexam-ethasone (FIG. 3 and 4). EPR lines of the individual groups of free radicals saturate at different microwave powers. Free radicals in sterilized dexamethasone are stabile. EPR studies indicate on small influence of microwave power on line asymmetry. Microwave power only slightly affects on all analyzed parameters IA1-A2I, IA1/A2I, IB1-B2I, IB1/B2I determined to evaluate line asymmetry.

13

Action of Some Organomercury Compounds on Photosynthesis in Spinach Chloroplasts

75%

Šeršeň F. , Kráľová K.

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tom Vol. 20, nr 3

489--498

EN

The effects of five organomercury compounds (methylmercuric chloride, phenylmercuric acetate, phenylmercuric borate, phenylmercuric citrate and diphenylmercury) on photosynthetic electron transport (PET) in spinach chloroplasts were investigated. The IC50 values of organomercury compounds related to PET inhibition in spinach chloroplasts varied in the range from 468 mmol dm-3 to 942 mmol dm-3 and were approximately by one order higher than the corresponding value determined for HgCl2 applied also in DMSO solution (IC50 = 58 mmol dm-3). Due to extremely low aqueous solubility of diphenylmercury, the corresponding IC50 value could not be determined. Using EPR spectroscopy as probable sites of action of organomercury compounds in photosynthetic apparatus ferredoxin on the acceptor side of PS 1 and the quinone electron acceptors QA or QB on the reducing side of PS 2 were suggested.

PL

Zbadano wpływ pięciu związków rtęcioorganicznych (chlorku metylortęci, octanu fenylortęci, boranu fenylortęci, cytrynianu fenylortęci i difenylortęci) na fotosyntetyczny transport elektronów (PET) w chloroplastach szpinaku. Wartości IC50 dla związków rtęcioorganicznych związanych z inhibicją PET w chloroplastach szpinaku zmieniała się w zakresie od 468 do 942 μmol dm-3 i była w przybliżeniu o rząd większa od odpowiedniej wartości określonej dla HgCl2, stosowanego również w roztworze DMSO (IC50 = 58 μmol dm-3). Ze względu na bardzo małą rozpuszczalność difenylortęci w wodzie odpowiednia wartość IC50 nie może być określona. Wyniki badań za pomocą spektroskopii EPR pozwoliły na zaproponowanie prawdopodobnych miejsc działania związków rtęci w procesie fotosyntezy ferredoksyny po stronie akceptora PS 1 i chinonowego akceptora elektronów QA lub QB po stronie redukującej PS 2.

14

Free radical formation in salicylic acid and heating parameters – application of EPR, UV-Vis, TGA and colorimetry examination to optimize thermal sterilization

75%

Ramos P. , Pilawa B.

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nr 3

431-441

EN

Salicylic acid heated at different temperatures and times was examined by an X-band (9.3 GHz) EPR spectroscopy, UV-Vis spectrophotometry, TGA and colorimetry test to optimize its thermal sterilization process. Free radical formation (~1018 spin/g) during thermal sterilization of salicylic acid according to the pharmaceutical norms at temperature 120oC and time of 120 minutes was compared with those for heating at the new tested temperatures and times: 130oC and 60 minutes, and 140oC and 30 minutes. It was obtained that the relatively lower free radical concentrations characterized salicylic acid heated at temperatures (times): 120oC (120 minutes), and 130oC (60 minutes), than at temperature (time) 140oC (30 minutes). So treatment at temperature 120oC during 120 minutes, and temperature 130oC during 60 minutes, were recommended as the optimal for thermal sterilization of salicylic acid. Salicylic acid should not be sterilized at temperature 140oC during 30 minutes, because of the highest free radical formation. Free radical systems of thermally treated salicylic acid revealed complex character. Fast spin-lattice relaxation processes existed in heated salicylic acid. Strong dipolar interactions characterized all the heated salicylic acid samples. EPR spectroscopy, UV-Vis spectrophotometry, thermogravimetry, and color measurement may be helpful besides microbiological analysis to optimize thermal sterilization conditions of salicylic acid.

15

Typy centrów paramagnetycznych a właściwości sprężyste i optyczne węgli kamiennych

63%

Pilawa B. , Pusz S. , Krzesińska M. , Kwiecińska B.

Karbo

|

2003

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tom Nr 4

224-227

PL

Wyznaczono dynamiczny moduł sprężystości, zdolność odbicia światła oraz parametry widm elektronowego rezonansu paramagnetycznego (EPR) dla szerokiego zakresu węgli kamiennych (83,5-94,9 % mas. C). Celem pracy było znalezienie różnych grup centrów paramagnetycznych w badanych węglach kamiennych oraz porównanie właściwości centrów paramagnetycznych z właściwościami elastycznymi i optycznymi próbek. W badanych węglach kamiennych znaleziono trzy różne grupy centrów paramagnetycznych, odpowiedzialne za szerokie linie Gaussa ( AB : 0,87-0,98 mT, g: 2,0031 -2,0037), szerokie linie Lorentza l (AB : 0,43-0,54 mT, g: 2,0030-2,0035) oraz wąskie linie Lorentza 2 (DeltaBpp: 0,08-0,14 mT, g: 2,0029-2,0030). Koncentracje centrów paramagnetycznych odpowiedzialnych za szerokie linie EPR malej ą wraz ze wzrostem anizotropii sprężystej węgla kamiennego. Szerokości linii wszystkich rodzajów centrów paramagnetycznych maleją ze wzrostem gęstości rzeczywistej węgla kamiennego. Zaobserwowano spadek wartości współczynnika g szerokiej linii Gaussa i szerokiej linii Lorentza l wraz ze wzrostem zawartości pierwiastka C w węglu oraz wraz ze wzrostem średniej zdolności odbicia światła węgla.

EN

Dynamic elastic moduli, optical reflectance and electron paramagnetic resonance (EPR) spectra parameters were determined for a wide rank coals (83,5-94,9 wt % C). The aim of this work was to find different groups of paramagnetic centers in the studied coals and to compare the feature of the paramagnetic centers with elastic and optical properties of coal. Three different groups of paramagnetic centers with broad Gauss (Delta Bpp 0,87-0,98 mT, g: 2,0031 -2,0037), broad Lorentz 1 (DeltaB: 0,43-0,54 mT, g: 2,0030-2,0035), and narrow Lorentzian 2 (AB : 0,08-0,14 mT, g: 2,0029-2,0030) lines were found in the studied coals. Concentrations of paramagnetic centers responsible for broad EPR lines decrease with increasing elastic anisotropy of coal. Linewidths of all types of paramagnetic centers decrease with increase of coal density. Decrease of g factor of broad Gauss and broad Lorentz 1 lines with increasing both a carbon content and mean reflectance was observed. KURZEJA L., MUSZYŃSKI J., DUBER S., SZELUGA U.: New carbon nanotubes/polymer composites and their properties.

16

Vibronic behaviour of octahedral Cu(II) complexes in Cu(2-benzoylpyridine)2(NO3)2x2H2O crystal with a weak superexchange coupling. Temperature EPR studies

63%

Hoffmann S. K. , Goslar J. , Hilczer W. , Goher M. A. S.

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2000

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tom Vol. 48, No. 4

397-409

EN

Octahedral [Cu(2-benzoylpyridine)2 (H20)2] complexes in the Cu(2-Bzpy)2-(NO3)2 .2H2O are very dynamical and Cu(II) ions are very weakly coupled as it is shown by the single crystal EPR measurements in the temperature range 4.2-300 K. Rigid lattice limit (9 K) of spin-Hamiltonian parameters are: gx = 2.137, gy = 2.014, gz = 2.306 as determined by decoupling of exchange merged EPR lines. The ground state is predominantly Ix(2) -y(2)) with 8% of the Iz(2)) state. This mixing is produced by zero-point motions in the ground vibrational state and results in g x > gy with strong lowering of the gy-value. The decoupling procedure gave superexchange coupling parameter J = 0.0040 cm(1), which unexpectedly is temperature independent in contrast to other weakly coupled Cu(II) paramagnets. The g-factors show relatively strong temperature variations with gy practically not affected by temperature and a tendency to averaging of the g x and gz with room tem-perature parameters: g x = 2.161, gy = 2.013, gz = 2.285. This is explained as the pseudo Jahn-1eller effect with dynamical transitions between two elongated octahedral axes, i.e. O-Cu-O (x-axis) and H2O-Cu-H2O (z-axis) with N-Cu-N (y-axis) direction ill the in-plane coordination with pyridine nitrogen not affected by vibronic dynamics. The vibronic effect can be described by two-well model in the temperature range 80-150 K only with energy difference between the ground vibronic state in the well being 220 cm-l. At lower temperatures Cu(II) complexes are strongly localized in the deepest potential well, whereas at higher temperatures, the vibronic g-factor averaging is dominated by the other mechanism.

17

EPR spectroscopic and rheological investigation during sol-gel transition in the systems TEOS/ethanol/water and sodium water-glass

63%

Breyer T. , Breitbarth F. W. , Vogelsberger W.

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2000

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tom Vol. 48, No. 4

325-336

EN

Paramagnetic ions (V4+ , Mn2+ ) are used to detect mobility changes during the sol-gel transition of sols from sodium water glass as well as from TEOS hydrolysis. The viscosity of these samples is measured in the rotational and oscillating mode to determine the steady state viscosity and the storage and loss moduli. The overall kinetic rate constant for the formation of siloxane bonds has been determined in dependence on pH of the reaction mixture. In spite of the rapid increase of the viscosity during the solgel transition by several orders of magnitude, EPR spectra of solvated VO2+ and Mn2+ probe ions do not show significant changes of the mobility. These ions move freely in the space between the agglomerating sol particles until the gels are dried. Paramagnetic V(IV) species derived from reduction of VO(iPr)3, however, are adsorbed on the growing sol particles. They, therefore, show a powder-like EPR spectrum of immobilized ions even in the region of very low sol viscosity well before the sol-gel transition.

18

Quantum chemical verification of new paramagnetic Mo(V) centre in MnO3

63%

Brocławik E. , Łabanowska M.

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2000

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tom Vol. 48, No. 4

303-311

EN

The aim of our work was independent verification of the proposed from EPR experiment uncommon nature of paramagnetic Mo(V) species lacking molybdenyl oxygene For this purpose quantum chemical DFT calculations have been carried out for [MoO(5)H8](3+) cluster model of reduced MOO3. Good agreement between the energy level diagram elucidated from EPR data with calculated orbital energies led to the conclusion that the structure of this Mo(V) centre seems to be well founded.

19

Badania Rhizoma calami metodą EPR

63%

Pawłowska-Góral K. , Kurzeja E. , Pilawa B. , Ramos P.

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2009

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tom Vol. 12, no. 89-91

159--161

PL

Przeprowadzono badania Rhizoma calami z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego (EPR) na pasmo X (9.3 GHz). Porównano koncentrację i właściwości centrów paramagnetycznych w próbkach wyjściowych oraz sterylizowanych parą wodną. Wykazano, że wolne rodniki występują w obydwu badanych próbkach roślinnych. Ciągłe nasycenie mikrofalowe linii EPR wykazało jednorodne rozmieszczenie wolnych rodników oraz wolne procesy relaksacji spin-sieć w Rhizoma calami.

EN

Rhizoma calami was examined by electron paramagnetic resonance (EPR) spectroscopy at X-band (9.3 GHz). Concentration and properties of paramagnetic centers in the original sample and sample sterilized by water vapour were compared. It was stated that free radicals exist in both the studied plant samples. Continuous microwave saturation of EPR lines proved homogeneous distribution of free radicals and slow spin-lattice relaxation processes in Rhizoma calami.

20

Zastosowanie spektroskopii EPR do badania wolnych rodników generowanych termicznie w drotawerynie

63%

Ramos P. , Pilawa B. , Adamski M.

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nr 1

28-37

EN

INTRODUCTION Microorganisms should be removed from drugs during their production, however, sterilization processes should not produce free radicals. Free radicals in drotaverine were studied. The applicability of thermal sterilization for drotaverine was investigated. MATERIAL AND METHODS Drotaverine heated to 160oC was examined by the EPR method. Free radical concentration, their distribution in the sample, the complex character of the free radical system and magnetic spin-spin interactions in the drug were determined. Changes in the free radical concentration in drotaverine during storage after sterilization also were examined. The sterilization conditions were chosen according to pharmakopeal norms. The analysed drug was sterilized in dry hot air. RESULTS EPR lines were not obtained for drotaverine before sterilization. It was demonstrated that drotaverine after thermal sterilization at temperature 160oC contains free radicals and exhibits EPR spectra. The free radical concen-tration in drotaverine changes with storage time after thermal treatment. Interactions with oxygen are probably responsible for this effect. The free radicals are homogeneously distributed in drotaverine since characteristic correlations between the amplitudes and linewidths of the EPR lines and microwave power were observed. The free radicals are closely located to one another in drotaverine and they strongly interact in a dipolar manner, which cause broadening of the EPR spectra. Continuous microwave saturation of the EPR spectra revealed that slow spin-lattice relaxation processes occur in thermally sterilized drotaverine. The shape of the EPR spectra and asymmetry parameters of the test drug change with increasing microwave power, indicating the complex nature of the free radicals in the sample. CONCLUSIONS Drotaverine should not be thermally sterilized because of free radical formation. The obtained results confirmed the usefulness of EPR spectroscopy to examine thermally sterilized drugs. The EPR method may be used as a supplement to microbiological tests.

PL

WSTĘP Leki wymagają usunięcia drobnoustrojów podczas ich produkcji, jednak procesy sterylizacji nie powinny generować wolnych rodników. Zbadano wolne rodniki w drotawerynie. Sprawdzono, czy sterylizacja termiczna może być w tym przypadku stosowana. MATERIAŁY I METODY Zbadano drotawerynę ogrzewaną w 160oC metodą EPR. Wyznaczono koncentrację wolnych rodników, określono sposób ich rozmieszczenia w ogrzanej próbce, złożoność układu wolnorodnikowego oraz oddziaływania magnetyczne spin-spin. Zbadano również zmiany koncentracji wolnych rodników w drotawerynie podczas przechowywania leku po sterylizacji. Warunki sterylizacji termicznej wybrano zgodnie z obowiązującymi normami farmakopealnymi. Lek sterylizowano suchym gorącym powietrzem. WYNIKI Nie uzyskano linii EPR dla drotaweryny przed sterylizacją. Wykazano, że drotaweryna po sterylizacji termicznej w temp. 160oC zawiera wolne rodniki i wykazuje widma EPR. Koncentracja wolnych rodników w drotawerynie zmienia się wraz z czasem przechowywania leku po obróbce termicznej. Za efekt ten odpowiadają prawdopodobnie oddziaływania z tlenem. Wolne rodniki w drotawerynie rozmieszczone są jednorodnie, ponieważ zaobserwowano charakterystyczne dla tego przypadku zależności amplitudy i szerokości linii EPR od mocy mikrofalowej. Wolne rodniki w drotawerynie są położone blisko siebie i silnie oddziałują dipolowo, co powoduje poszerzenie widm EPR. Ciągłe nasycenie mikrofalowe widm EPR wykazało, że w drotawerynie sterylizowanej termicznie zachodzą wolne procesy relaksacji spin-sieć. Kształt widm EPR i parametry asymetrii testowanego leku zmieniają się wraz ze wzrostem mocy mikrofalowej, co wskazuje na złożony charakter układu wolnych rodników w próbce. WNIOSKI Drotaweryna nie powinna być sterylizowana termicznie ze względu na generowanie wolnych rodników. Uzyskane rezultaty potwierdziły przydatność spektroskopii EPR do badania leków sterylizowanych termicznie. Metoda EPR może być wykorzystana jako uzupełnienie testów mikrobiologicznych.